US2652129A - Separation of mixed gases by absorption - Google Patents

Separation of mixed gases by absorption Download PDF

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US2652129A
US2652129A US747019A US74701947A US2652129A US 2652129 A US2652129 A US 2652129A US 747019 A US747019 A US 747019A US 74701947 A US74701947 A US 74701947A US 2652129 A US2652129 A US 2652129A
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gases
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Benedict Manson
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Hydrocarbon Research Inc
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D53/00Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/14Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by absorption

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  • the present invention relates to the separation of components of a gas mixture by countercurrent absorption in a liquid absorbent in which the components have differing solubilities, and contemplates operation at improved efficiency and with a reduced net work input. It is particularly concerned with charging lean absorp tion liquid to the top of an absorption column in such a manner as to permit recovering in useful form, work potentially available in saturating the liquid with the gases present at the top of the column.
  • stripped absorption liquid is charged at the top of the absorption column in order to dissolve a portion of the gas mixture which then serves as reflux in effecting the desired separation.
  • the gas mixture is allowed to dissolve irreversibly in the stripped liquid at the top of the column without producing useful work.
  • solution of gas is carried out at the top of the column in the absorption liquid under approximately reversible conditions so that useful work which is ordinarily wasted is realized at this point in the process.
  • reversible as applied to a process step is used to mean that the step is so conducted as to require the least work input (or to permit recovery of maximum work output) consistent with the limitations placed on the process step by thermodynamics.
  • all flow of heat and matter takes place between parts of a system in approximate thermodynamic equilibrium with each other.
  • An example of a reversible process step is the dissolving of a gas in a liquid already substantially saturated by the gas.
  • an irreversible process step In an irreversible process step more work must be supplied (or less work recovered) than the amount predicted by thermodynamics for a reversible process step.
  • Typical examples of an irreversible process step are the mixing of materials which are substantially not in thermodynamic equilibrium, the flow of heat through a substantial temperature difference, and the diffusion of gases through a substantial concentration difierence.
  • a suitable absorbing liquid flows down in countercurrent relationship to the upward-flowing gaseous mixture to be separated. Because of the difference in solubility of the components of the gas mixture, the liquid becomes progressively and selectively enriched in the more soluble components as it progresses down the column. Rich liquid, withdrawn from the bottom of the fractionating zone of the column, containing a substantial, selected proportion of dissolved gas of relatively high solubility, is subjected to treatment adapted to disengage contained product gas, leaving the residual liquid in lean condition suitable for return to the top of the fractionating zone. Direct charging of this stripped lean absorbing liquid at the top of the zone into contact with the stream of tops gas would result in substantial loss of potentially available work which could be recovered if the liquid were brought into contact with the gas under reversible conditions.
  • gas from the top of the fractionating zone is expanded to a lower pressure stage in an engine to recover useful work
  • the expanded gas is contacted with the absorbing liquid in the lower pressure stage so as to saturate the absorbing liquid at least partially with the gas.
  • the lower pressure stage thus acts as a saturating step for the absorbing liquid which is being returned to the iractionating zone.
  • the invention is broadly applicable to any absorption system wherein a lean absorbent liquid is introduced into a fractionating zone operating at any substantial pressure, it is particularly advantageous in connection with separations wherein absorption and disengagement are effected primarily through changes in pressure; that is, where the variation of gas solubility in the liquid with temperature is so slight as to require that absorption and disengagement be effected essentially by a change in pressure.
  • the invention finds special application in the separation of at least semi-permanent gases, which term is intended to include preferably the permanent gases as well as those gases, the critical point of which is below about F., which possess a characteristically low temperature coefficient of solubility.
  • the present invention is particularly applicable to absorption systems acting upon a gas mixture where the difierence in solubility between the components of the mixture is slight.
  • the work potentially recoverable through reversible solution increases quite materially as the solubilities of the gases to be separated approach each other.
  • the benefit therefore is particularly pronounced where the relative volatility of the component gases in the liquid absorbent, expressed as the ratio of the volume solubility of the more soluble to the less soluble component, is not substantially greater than about 2.0 (2:1) and preferably less than about L5 ('l.5:1).
  • the numeral H] represents a gas-liquid contact tower comprising a rectifying or enriching section II, a stripping section l2, 2. disengaging section I3, and a saturating section 14.
  • Sections H and I2 taken together comprise the main fractionating zone in which the principal separation or the components of the gas mixture occurs. Further fractionation of the components of the gas mixture occurs in sections l3 and M, accompanied by solution of gas in M and separation of gas in I3.
  • each of the column sections may be of typical packed tower or bubble tower arrangement comprising vertically spaced trays through which the downcoming oil successively passes in good surface contact with upflowing gases.
  • the mixed feed gases are introduced to a lower portion of the enriching section II from any convenient source not shown through pipe l5 by way of a compressor I6, delivering at elevated column pressure, and a cooling heat exchanger ll which brings the hot compressed gases to the desired column temperature, as for example, 100 F.
  • the enriched oil continues to pass downwardly through the stripping secion l2, where the dissolved gas is further enriched in the more soluble component, and is withdrawn near the base thereof through outlet pipe [9, passed through a suitable engine 20, suchas a Pelton wheel, at a substantially lower pressure and introduced into the top of the disengaging section [3 through pipe 21.
  • the pressure in section i3 is some intermediate pressure between that of the main column or fractionation zone, and the final pressure of disengagement.
  • the oil After passing through the section I3 at an intermediate pressure, the oil is withdrawn through pipe 25, passed through a second impulse engine 26 to a lower, intermediate pressure level with the recovery of mechanical work, and introduced by pipe 21 into a flash drum 28.
  • the flash drum 28 operates at that lower pressure which causes the disengagement of a quantity of absorbed gases sufficient to strip light gas dissolved in the liquid flowing through sections 12 and I3.
  • This gas is withdrawn through pipe 29, recompressed to the pressure of section [3 by compression means 36, cooled to tower temperature in exchanger SI, and conveyed by pipe 32 to alower portion of the disengaging section l3, where it passes upwardly in countercurrent relation to the downfiowing rich oil.
  • it tends to additionally strip or disengage the less soluble component of the gas mixture with resulting enrichment of the oil in the desired gaseous constituent of greater solubility.
  • Gaseous eiiluent from the top of section I3 is withdrawn as at 33, compressed to the operating pressure of the main tower sections by compressor 34, and cooled to tower temperature by exchanger thence passing directly into the lower part of the stripping section by way of conduit 36.
  • flash drum 4i operates at substantially atmospheric pressure, whereby the disengaged gas withdrawn through pipe 43 is delivered, at a convenient pressure, as essentially pure or enriched bottoms product gas.
  • is withdrawn as at M, and passed through throttle valve 45 into a final flash drum 4? operating at a suitably low vacuum, as for example, 2 p. s. i. a.
  • a suitably low vacuum as for example, 2 p. s. i. a.
  • the resulting lean oil from the flash drum 4? is passed through recycle conduit 52 by a lean oil pump 53, to the top of the tower for continuous repetition of the separation process.
  • the upper or reversible saturating section M of the tower comprises, in the present embodiment, three separate saturation sections or stages operating at appropriate intermediate pressures between the low pressure of final disengagement and operating pressure of the enriching section.
  • the upper or first saturation section 55 receives the incoming lean oil by way of pipe 54, at a suitable initial pressure, where it flows downwardly countercurrent to upflowing tops gas, and is withdrawn at 53 and injected into the upper portion of a' second stage saturation section 51 by pump 58 and inlet pipe 59.
  • the stream of oil is withdrawn from a lower portion as at BI), and passed by pump ti and inlet pipe 62, into a third saturation section 63, operating at a pressure intermediate between that of the second stage section and the pressure of the enriching section.
  • the stream withdrawn as at 64 is raised to main tower pressure by pump 65, and injected into the upper portion of the enriching section through inlet pipe 66.
  • Useful work realized in the expansion engine H may be utilized for any desired purpose.
  • the stream of gas is first supplied with thermal energy in heat exchanger '12, whereby a more or less regular column temperature is maintained, and a correspondingly increased recovery of mechanical Work. realized in the expansion engine H.
  • gaseous product of the second stage is removed as at 11, passed through heating exchanger 13, and expander l9, and injected into the upper or initial saturation stage 55 through pipe 80.
  • the gas withdrawn from the top portion of this stage through outlet pipe 8! comprises separated product rich in the less soluble constituent of the feed.
  • valved branch pipe 85 which communicates with pipe !8.
  • Available mechanical energy may be recovered from the relatively high pressure gas stream in pipe by passage through heat exchanger 8t and expansion engine 81 as before.
  • cooling exchangers l'i, 3!, 35 and 58 in the usual case, handle heat energy amply suificient for this purpose.
  • Interconnection of the several heat exchangers for this purpose has not been shown since the many possible variations thereof are within the province of any skilled engineer, and further, because the complex details might obscure a, clear understanding of the principles of the present invention.
  • a suitable heat exchange liquid such as water, Dowtherm or mercury passes countercurrently to the gas stream through any or all of the aforementioned coolers and is thereafter pumped through the heating exchangers 12, 14, 18 and 36, preferably counterourrent to the stream of gases for transferring thermal energy thereto in any desired rate.
  • the lean oil supplied to the tower is progressively saturated with product gas in a series of stages of relatively increasing pressure such that solution takes place under conditions more closely approaching equilibrium than in the case where lean oil is charged directly into an absorption tower and operating pressure.
  • the conditions even more closely approach thermodynamic equilibrium with its corresponding high efficiency of reversible absorption. It follows therefore that potentially available work otherwise lost or consumed in the irreversible saturation of lean oil with tops gas at th elevated pressure of the enriching section, is recovered as useful work in the expansion engines il, 75 and is, and that moreover the total useful work thus recoverable increases with the number of saturating stages at intermediate pressures. As further intimated above, the work thus recoverable may be substantial.
  • the pressure in the enriching and stripping sections of the column is 300 p. s. i. a., and the tower and flash drums are maintained at substantially F. throughout.
  • the absorbing liquid comprises a narrow range paraffinic absorption oil of about 38 A. P. I. gravity, and a molal average boiling point of 500 F., supplied to the tower at the rate of about 18 cubic feet (about 4.42 mols) per mol of feed gas. This involves a lean oil rate of about 1.5 times the minimum lean oil rate at which separation will take place under conditions of highest thermodynamic efficiency.
  • the feed and product gases are respectively supplied and withdrawn at atmospheric pressure and 100 F.
  • the saturation or absorption of the tops gas in the lean oil is carried out in three stages, as in the above embodiment at appropriate, successively increasing pressures intermediate between the lowest lean oil pressure and that of the main section of the tower. More specifically, the three saturating sections operate, in the order of introduction of the lean oil thereto, at the following pressures:
  • Each comprises one bubble tray;
  • Theenriching section contains 21 trays, and-the stripping section 8 trays.
  • the lower portion of the tower is provided with a disengagingsection-containing erating respectively at atmospheric pressure and- 2 p. s. i. a. with discharge of the bottom product gas at atmospheric pressure and 100 F. as noted above.
  • Th impulse engines recover the usefulmechanical work in conducting the oil stream from the stripping section to the succeeding disengaging section, and the succeedin flash'drums.
  • the system is designed to deliver, from the top of the first or initial oil saturating-section; a product containing approximately 95 mol percent ethylene and 5 mol percent ethane and a'bottoms product gas'having the approximate composition of 91.8% ethane, and 8.2% ethylene on a molar basis.
  • the foregoing example discloses a net saving of 593,000 foot pounds of mechanical work per mol of feed gas in the process herein disclosed as compared with a process where the lean oil is charged directly at main column pressure. This may be compared with the approximately 389,000 foot pounds per mol of feed gas mini-' mum thermodynamic work necessary to efiect this separation. The remainder of the work expended is, of course, dissipated through compressor and expander inei'iiciencies and irreversible losses elsewhere in the system.
  • the specific absorbing liquid, perse, forms'no part of the present invention, and may beselected with due regard to the controlling factors" of solubility and conventional practices known to those skilled inthe art, taking into consideration the character of the gases to be separated.
  • the improvement is particularly' valuable in'the case of so-call'cdisothermal absorption, it may be'broadlypracticed,
  • the present invention is moreover not limited to the particular method for disengagement specifically exemplified.
  • the invention contemplates, for example, adaptation and incorporation of conventional, though less eificient procedures for recovery of the absorbed gas from rich absorbing liquid withdrawn from the main column sections.
  • Such conventional procedures are exemplified by single stage decompression, heating, distillation, extraction, or otherwise. The lean oil after decompression is then made available for recycle to the successive saturation stages as disclosed.
  • the several engines or any combination thereof may advantageously be mechanically interconnected to deliver work from a common drive means.
  • the several expansion engines recovering useful work from the expanding gases may be disposed on a common shaft or axially interconnected for application of their combined output to the actuation of any unitary means, not shown, requiring the expenditure of mechanical work.
  • the improvement of recovering the potentially available work otherwise consumed in the irreversible absorption of tops gas from said fractionating zone in lean liquid absorbent at the pressure of said fractionating zone which comprises expanding said tops gas to a lower pressure with the performance of work, contacting said lean liquid absorbent with the expanded gas at said lower pressure to dissolve part of said expanded gas in said lean liquid absorbent, supplying said liquid absorbent containing dissolved gas to said fractionating zone, and recovering the work performed in expanding said tops gas.
  • Apparatus for the separation of mixed gases of different solubilities by fractionating enrichment of a stream of said gases flowing in countercurrent contacting relationship under pressure, with a stream of absorbing liquid effective to preferentially absorb relatively more soluble gas including fractionating means for conducting said stream of mixed gases under pressure in countercurren-t contacting relationship with a stream of absorbing liquid, a plurality of expansion engines eifective to recover useful mechanical work from expanding gas, means for supplying eiliuent undissolved gas from said fractionating means to said expansion engines in successive series relationship, means for dissolving expanded gas from a succeeding expansion engine in lean absorbing liquid to effect at least partial saturation thereof, means thereafter for dissolving additicnal expanded gas from a preceding expansion engine in said partially saturated absorbing liquid, and means for introducing thus partially saturated absorbing liquid as liquid absorbent to said fractionating zone as aforesaid.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Analytical Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Gas Separation By Absorption (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Description

S p 15, 1953 M. BENEDICT 2,652,129
SEPARATION OF MIXED GASES Y ABSORPTION Filed May 9, 1947 Way I INVEN TOR. MA/vso/v BENEDICT ATTORNE Y5 Patented Sept. 15, 1953 2,652,129 I C E SEPARATION OF MIXED GASES BY ABSORPTION Manson Benedict, Westfield, N. J., assignor to Hydrocarbon Research, Inc., New York, N. Y., a corporation of New Jersey Application May 9, 1947, Serial No. 747,019
14 Claims.
The present invention relates to the separation of components of a gas mixture by countercurrent absorption in a liquid absorbent in which the components have differing solubilities, and contemplates operation at improved efficiency and with a reduced net work input. It is particularly concerned with charging lean absorp tion liquid to the top of an absorption column in such a manner as to permit recovering in useful form, work potentially available in saturating the liquid with the gases present at the top of the column.
In absorption processes for separating the constituents of a mixture which is gaseous at the desired operating conditions, stripped absorption liquid is charged at the top of the absorption column in order to dissolve a portion of the gas mixture which then serves as reflux in effecting the desired separation. As ordinarily practiced, the gas mixture is allowed to dissolve irreversibly in the stripped liquid at the top of the column without producing useful work.
In accordance with the present invention, solution of gas is carried out at the top of the column in the absorption liquid under approximately reversible conditions so that useful work which is ordinarily wasted is realized at this point in the process.
The term, reversible, as applied to a process step is used to mean that the step is so conducted as to require the least work input (or to permit recovery of maximum work output) consistent with the limitations placed on the process step by thermodynamics. In reversible processes, all flow of heat and matter takes place between parts of a system in approximate thermodynamic equilibrium with each other. An example of a reversible process step is the dissolving of a gas in a liquid already substantially saturated by the gas.
In an irreversible process step more work must be supplied (or less work recovered) than the amount predicted by thermodynamics for a reversible process step. Typical examples of an irreversible process step are the mixing of materials which are substantially not in thermodynamic equilibrium, the flow of heat through a substantial temperature difference, and the diffusion of gases through a substantial concentration difierence.
In the absorption column, a suitable absorbing liquid flows down in countercurrent relationship to the upward-flowing gaseous mixture to be separated. Because of the difference in solubility of the components of the gas mixture, the liquid becomes progressively and selectively enriched in the more soluble components as it progresses down the column. Rich liquid, withdrawn from the bottom of the fractionating zone of the column, containing a substantial, selected proportion of dissolved gas of relatively high solubility, is subjected to treatment adapted to disengage contained product gas, leaving the residual liquid in lean condition suitable for return to the top of the fractionating zone. Direct charging of this stripped lean absorbing liquid at the top of the zone into contact with the stream of tops gas would result in substantial loss of potentially available work which could be recovered if the liquid were brought into contact with the gas under reversible conditions.
In accordance with the present invention, a substantial portion of this potentially available work is recovered in useful form by dissolving the gas in the absorbing liquid under nearly reversible conditions.
To this end, gas from the top of the fractionating zone is expanded to a lower pressure stage in an engine to recover useful work, the expanded gas is contacted with the absorbing liquid in the lower pressure stage so as to saturate the absorbing liquid at least partially with the gas. The lower pressure stage thus acts as a saturating step for the absorbing liquid which is being returned to the iractionating zone. To recover more of the work potentially available, it is advisable to employ a plurality of saturating stages or zones arranged in series and maintained at progressively lower pressures in the direction of gas flow or progressively higher pressures in the direction of absorbing liquid flow. It is clear that the larger the number of saturating stages in each of which gas expanded from a higher pressure contacts liquid pumped from a lower pressure, the more truly reversible becomes the operation.
Obviously, from the foregoing, with an increase in the number of expansion stages, useful mechanical Work recovered approaches that potentially available in saturating lean oil with gas, which is otherwise consumed or wasted in the irreversible absorption of gas in lean oil of the column pressure. The potentially recoverable Work lost in irreversible steps involved in the charging of lean oil at column pressure in typical gases is often greater than the minimum reversible work of separation.
While the invention is broadly applicable to any absorption system wherein a lean absorbent liquid is introduced into a fractionating zone operating at any substantial pressure, it is particularly advantageous in connection with separations wherein absorption and disengagement are effected primarily through changes in pressure; that is, where the variation of gas solubility in the liquid with temperature is so slight as to require that absorption and disengagement be effected essentially by a change in pressure. In short the invention finds special application in the separation of at least semi-permanent gases, which term is intended to include preferably the permanent gases as well as those gases, the critical point of which is below about F., which possess a characteristically low temperature coefficient of solubility. For the purpose of the present specification and claims, the process whereby absorptive separation is effected essen-' tially by solution of the gas at a higher pressure and disengagement at a lower pressure is referred to as isothermal absorption, whether or not temperature variations are incidentally in-' volved.
The present invention is particularly applicable to absorption systems acting upon a gas mixture where the difierence in solubility between the components of the mixture is slight. In fact, the work potentially recoverable through reversible solution increases quite materially as the solubilities of the gases to be separated approach each other. The benefit therefore is particularly pronounced where the relative volatility of the component gases in the liquid absorbent, expressed as the ratio of the volume solubility of the more soluble to the less soluble component, is not substantially greater than about 2.0 (2:1) and preferably less than about L5 ('l.5:1). A
In order to describe the invention more in dedetail, reference is now made to the accompanying drawing where one exemplary embodiment is disclosed more or less diagrammatically for the purpose of simplifying understanding of the invention.
In the drawing, the numeral H] represents a gas-liquid contact tower comprising a rectifying or enriching section II, a stripping section l2, 2. disengaging section I3, and a saturating section 14. Sections H and I2 taken together comprise the main fractionating zone in which the principal separation or the components of the gas mixture occurs. Further fractionation of the components of the gas mixture occurs in sections l3 and M, accompanied by solution of gas in M and separation of gas in I3.
In order to further facilitate specific description of the embodiment, reference thereto will be made in terms of a process employing an absorption liquid comprising a suitable hydrocarbon oil capable of absorbing feed gas under elevated pressure and appropriate temperature. Each of the column sections may be of typical packed tower or bubble tower arrangement comprising vertically spaced trays through which the downcoming oil successively passes in good surface contact with upflowing gases. I
The mixed feed gases are introduced to a lower portion of the enriching section II from any convenient source not shown through pipe l5 by way of a compressor I6, delivering at elevated column pressure, and a cooling heat exchanger ll which brings the hot compressed gases to the desired column temperature, as for example, 100 F.
In the enriching section the gases pass upwardly, while the gases dissolved in the downcoming oil are progressively enriched in the more soluble component. The tops gas, thus highly concentrated in relatively less soluble gas, is withdrawn through outlet pipe l8 for treatment, as will hereinafter be described in more detail.
The enriched oil continues to pass downwardly through the stripping secion l2, where the dissolved gas is further enriched in the more soluble component, and is withdrawn near the base thereof through outlet pipe [9, passed through a suitable engine 20, suchas a Pelton wheel, at a substantially lower pressure and introduced into the top of the disengaging section [3 through pipe 21. The pressure in section i3 is some intermediate pressure between that of the main column or fractionation zone, and the final pressure of disengagement.
After passing through the section I3 at an intermediate pressure, the oil is withdrawn through pipe 25, passed through a second impulse engine 26 to a lower, intermediate pressure level with the recovery of mechanical work, and introduced by pipe 21 into a flash drum 28. Preferably the flash drum 28 operates at that lower pressure which causes the disengagement of a quantity of absorbed gases sufficient to strip light gas dissolved in the liquid flowing through sections 12 and I3. I
This gas is withdrawn through pipe 29, recompressed to the pressure of section [3 by compression means 36, cooled to tower temperature in exchanger SI, and conveyed by pipe 32 to alower portion of the disengaging section l3, where it passes upwardly in countercurrent relation to the downfiowing rich oil. Here it tends to additionally strip or disengage the less soluble component of the gas mixture with resulting enrichment of the oil in the desired gaseous constituent of greater solubility.
Gaseous eiiluent from the top of section I3 is withdrawn as at 33, compressed to the operating pressure of the main tower sections by compressor 34, and cooled to tower temperature by exchanger thence passing directly into the lower part of the stripping section by way of conduit 36.
Referring now to the liquid product of flash drum 28, this is withdrawn through pipe 40 and reduced to the lower pressure of flash drum 4!, by passage through a further impulse engine 42 effective to deliver useful mechanical work.
While, as intimated above, any desired number of expansion stages may be employed, the present embodiment discloses an arrangement wherein flash drum 4i operates at substantially atmospheric pressure, whereby the disengaged gas withdrawn through pipe 43 is delivered, at a convenient pressure, as essentially pure or enriched bottoms product gas. To effect a further disengagement of absorbed bottoms gas, the residual oil from flash drum 4| is withdrawn as at M, and passed through throttle valve 45 into a final flash drum 4? operating at a suitably low vacuum, as for example, 2 p. s. i. a. Therein, occurs substantially complete disengagement of absorbed bottoms gas, which passes out through pipe 48, compressor 49, and cooling heat exchanger 58 into the outlet header or conduit 43 at atmospheric pressure.
The resulting lean oil from the flash drum 4? is passed through recycle conduit 52 by a lean oil pump 53, to the top of the tower for continuous repetition of the separation process.
As above indicated, the upper or reversible saturating section M of the tower comprises, in the present embodiment, three separate saturation sections or stages operating at appropriate intermediate pressures between the low pressure of final disengagement and operating pressure of the enriching section. Accordingly, the upper or first saturation section 55 receives the incoming lean oil by way of pipe 54, at a suitable initial pressure, where it flows downwardly countercurrent to upflowing tops gas, and is withdrawn at 53 and injected into the upper portion of a' second stage saturation section 51 by pump 58 and inlet pipe 59. Passing clown wardly through the second stage at an increased intermediate pressure, the stream of oil is withdrawn from a lower portion as at BI), and passed by pump ti and inlet pipe 62, into a third saturation section 63, operating at a pressure intermediate between that of the second stage section and the pressure of the enriching section. After passage downwardly through the section 63, the stream withdrawn as at 64 is raised to main tower pressure by pump 65, and injected into the upper portion of the enriching section through inlet pipe 66.
The tops gas or effluent from the enrichment section, rich in the less soluble constituent of the initial feed, is withdrawn through the previously mentioned outlet pipe 58 and passed through an expansion engine H, into a lower portion of the third saturation stage 63. Useful work realized in the expansion engine H may be utilized for any desired purpose.
Advantageously, in so-called isothermal absorption operations such as that herein selected for the purpose of illustration, the stream of gas is first supplied with thermal energy in heat exchanger '12, whereby a more or less regular column temperature is maintained, and a correspondingly increased recovery of mechanical Work. realized in the expansion engine H.
In the third stage gas-liquid contactor increased saturation of oil is effected, and the residual gas is withdrawn through pipe 13, pref- U erably passed through a second heating ex changer i4, and then through a second expansion engine '55, operating as before to recover mechanical work and discharge the gaseous stream through pipe 16 into the lower portion of the second saturation stage at appropriate temperature and pressure.
In the same manner the gaseous product of the second stage is removed as at 11, passed through heating exchanger 13, and expander l9, and injected into the upper or initial saturation stage 55 through pipe 80. The gas withdrawn from the top portion of this stage through outlet pipe 8! comprises separated product rich in the less soluble constituent of the feed.
Many other variations in the above embodiment will be apparent to those skilled in the art in light of the foregoing disclosure. For example, instead of passing the entire gaseous effiuent from the enriching section through the lean oil saturation sections, the main flow of light product gas or any portion thereof can be withdrawn through valved branch pipe 85 which communicates with pipe !8. In this modification, it is, of course, advantageous to pass at least sufficient of the gas through the saturation stages so that maximum saturation of the incoming oil is effected. Available mechanical energy may be recovered from the relatively high pressure gas stream in pipe by passage through heat exchanger 8t and expansion engine 81 as before.
It is particularly important to note that the low grade heat requirements of the heating exchangers 12, M, and 18 as well as exchanger 86 are readily met by the available heat recovered in the process. Thus, for example, cooling exchangers l'i, 3!, 35 and 58, in the usual case, handle heat energy amply suificient for this purpose. Interconnection of the several heat exchangers for this purpose has not been shown since the many possible variations thereof are within the province of any skilled engineer, and further, because the complex details might obscure a, clear understanding of the principles of the present invention. Nevertheless, the invention clearly contemplates such an arrangement as, for example, where a suitable heat exchange liquid such as water, Dowtherm or mercury passes countercurrently to the gas stream through any or all of the aforementioned coolers and is thereafter pumped through the heating exchangers 12, 14, 18 and 36, preferably counterourrent to the stream of gases for transferring thermal energy thereto in any desired rate.
In the foregoing embodiment, it will be apparent that the lean oil supplied to the tower is progressively saturated with product gas in a series of stages of relatively increasing pressure such that solution takes place under conditions more closely approaching equilibrium than in the case where lean oil is charged directly into an absorption tower and operating pressure. As indicated above, with increase in the number of saturation stages, the conditions even more closely approach thermodynamic equilibrium with its corresponding high efficiency of reversible absorption. It follows therefore that potentially available work otherwise lost or consumed in the irreversible saturation of lean oil with tops gas at th elevated pressure of the enriching section, is recovered as useful work in the expansion engines il, 75 and is, and that moreover the total useful work thus recoverable increases with the number of saturating stages at intermediate pressures. As further intimated above, the work thus recoverable may be substantial.
For instance, an example will be given of an absorption system employing substantially the arrangement described above as applied to the separation of a gaseous feed comprising ethylene and ethane in approximately the following proportion:
The pressure in the enriching and stripping sections of the column is 300 p. s. i. a., and the tower and flash drums are maintained at substantially F. throughout.
The absorbing liquid comprises a narrow range paraffinic absorption oil of about 38 A. P. I. gravity, and a molal average boiling point of 500 F., supplied to the tower at the rate of about 18 cubic feet (about 4.42 mols) per mol of feed gas. This involves a lean oil rate of about 1.5 times the minimum lean oil rate at which separation will take place under conditions of highest thermodynamic efficiency.
For purposes of affording a fair relative evaluation, the feed and product gases are respectively supplied and withdrawn at atmospheric pressure and 100 F. The saturation or absorption of the tops gas in the lean oil is carried out in three stages, as in the above embodiment at appropriate, successively increasing pressures intermediate between the lowest lean oil pressure and that of the main section of the tower. More specifically, the three saturating sections operate, in the order of introduction of the lean oil thereto, at the following pressures:
1 Atmospheric pressure.
Each comprises one bubble tray; Theenriching section contains 21 trays, and-the stripping section 8 trays. The lower portion of the tower is provided with a disengagingsection-containing erating respectively at atmospheric pressure and- 2 p. s. i. a. with discharge of the bottom product gas at atmospheric pressure and 100 F. as noted above. Th impulse engines recover the usefulmechanical work in conducting the oil stream from the stripping section to the succeeding disengaging section, and the succeedin flash'drums.
The system is designed to deliver, from the top of the first or initial oil saturating-section; a product containing approximately 95 mol percent ethylene and 5 mol percent ethane and a'bottoms product gas'having the approximate composition of 91.8% ethane, and 8.2% ethylene on a molar basis.
Following is a table showing design relationships, neglecting heat of absorption and descr ption of the'feed gases and assuming isothermal expansion and compression, between the work, in foot pounds per mol of feed gas, required for operation of the above system, with particular reference to the saturating instrumentalities, and the useful work recovered, under an operational eificiency allowance of 70% for the expansion engines and compressor, and 85% for the oil pumps.
Ft. lbs. per mol Feed Gas Work Sup- Wbrk 2 92213 Recovered Compression of feed gas from atmospheric to 300 p. s. i. a .1 3, 074,000 Lean Oil compression:
Recycle lean oil pump, 38,100 foot pounds Oil pump to second stage, 76,200 foot pounc s 0 Oil pump to third stage, 212 00 pounds,- Oil pump to enriching scc foot pounds Useful work delivered by tops gas expanders:
Expansion to third stage, 720,000 foot pounds .s .21 4 6; Expansion sccon stage, 07, 0
foot pounds 1'494'00O Expansion to first stage, 331,000 foot pounds Compression of bottoms gas: I
First stage decompression to stripping section, 2,019,000.... Second stage flash drum to first stage 3 874 000 decompression section, 1,028,000..- Final flash drum to atmospheric,
227,000 Useful work delivered by Pelton-wheel Expansion to first stage, 320,000. Expansion to second stage drum,
175,000 587, 100 Expansion to third stage atmospheric drum, 83, ;.l.
Totals 7, 865, 300 2, 081, 100
Not Work 5, 78 200 For purposes of contrast, there follows a similar table comparing the design characteris- The gaseous eiiluent from tics of a comparable absorption system in which the-lean oil is chargeddirectly at column pressure and temperature without reversible saturation intothe upper portion of the enriching zone in the vicinity of the point of withdrawal of the tops gaseous product, which is heated as required, and passed through a similar expansion engine, delivering at atmospheric pressure and F., for the recovery of potentially available mechanical work. In this case, conditions and apparatus are otherwise the same as in the example, except that the enriching section of the tower employs 18 trays and stripping section 8 trays whereby an indentical product separation is effected.
Ft. lbs. per mol Feed Gas gf gf Work System Recovered Compression of feed gas from atmospheric to 300 p. s. i. a 3, 074,000 Lean oil compressiom. 00 Expansion of tops gas 879, 000 Compression of bottoms gas:
First stage decompression to stripping section, 2,610,000 Second stage flash drum to first stage 3 874 000 decompression section, 1,028,000.-.. Finel flash drum to atmospheric, 227,000 Useful work delivered by Pelton wheels:
Expansion to first stage, 329,000 Expansion to second stage drum,
175,000 587,100 Expansion to third stage atmospheric drum, 83,100... ..i
Totals 7, 843, 000 1, 466, 100
Net Work 6, 370, 900
The foregoing example discloses a net saving of 593,000 foot pounds of mechanical work per mol of feed gas in the process herein disclosed as compared with a process where the lean oil is charged directly at main column pressure. This may be compared with the approximately 389,000 foot pounds per mol of feed gas mini-' mum thermodynamic work necessary to efiect this separation. The remainder of the work expended is, of course, dissipated through compressor and expander inei'iiciencies and irreversible losses elsewhere in the system.
While the invention has been particularly disclosed in connection with separation of ethyleneethane mixtures, it is applicable to any process of gas absorption separation of which I am aware, and particularly those wherein absorption and disengagement are effected principally by means of change in pressure. Accordingly, any mixture of feedgases of close relative solubility may be thus separated and as intimated above, the work recovery becomes highly significant where the ratio of solubilities approaches unity, as for example, in the separation of hydrogen, from deuterium, or of methane containing carbon- 13 from ordinary methane.
Obviously, the specific absorbing liquid, perse, forms'no part of the present invention, and may beselected with due regard to the controlling factors" of solubility and conventional practices known to those skilled inthe art, taking into consideration the character of the gases to be separated. Thus, while the improvement is particularly' valuable in'the case of so-call'cdisothermal absorption, it may be'broadlypracticed,
usually with some'material benefit, in any type of absorption process wherein a gaseous stream conditions otherwise sufliciently remote from equilibrium, so that useful work, during solution of gas in liquid, can be produced by the means described herein.
The present invention is moreover not limited to the particular method for disengagement specifically exemplified.
In its broadest aspect, the invention contemplates, for example, adaptation and incorporation of conventional, though less eificient procedures for recovery of the absorbed gas from rich absorbing liquid withdrawn from the main column sections. Such conventional procedures are exemplified by single stage decompression, heating, distillation, extraction, or otherwise. The lean oil after decompression is then made available for recycle to the successive saturation stages as disclosed.
It is particularly important to note that the several engines or any combination thereof may advantageously be mechanically interconnected to deliver work from a common drive means. For example, the several expansion engines recovering useful work from the expanding gases may be disposed on a common shaft or axially interconnected for application of their combined output to the actuation of any unitary means, not shown, requiring the expenditure of mechanical work.
Obviously many modifications and variations of the invention as hereinbefore set forth, may be made without departing from the spirit and scope thereof, and therefore only such limitations should be imposed as are indicated in the appended claims.
I claim:
1. In the separation of mixed gases of different solubilities by continuous fractionating absorption in contact with a stream of absorbing liquid under conditions including a pressure effective to cause selective enrichment of the absorbed gases in the more soluble component of the said mixed gases, followed by disengagement of absorbed gas from the absorbing liquid, and return of the lean absorbing liquid for fractionation of said mixed gases, the steps which comprise passing said mixed gases in a fractionating zone under pressure in contacting relation to the absorbing liquid, withdrawing undissolved gas from the absorbing liquid after contact therewith at said pressure, reversibly expanding withdrawn gas to a lower pressure level and at said lower pressure effecting absorbing of the expanded gas in the lean absorption liquid under conditions approaching equilibrium, recovering mechanical work of expanding the gas, and supplying the thus partially saturated absorbing liquid to passage in contact with said mixed gases in said fractionating zone under pressure as said absorbing liquid.
2. The method defined in claim 1 wherein reversible expansion of the withdrawn gas and the absorption of the expanded gas in the lean liquid absorbent is carried out in a plurality of stages of successively lower pressure.
3. The method defined in claim 1 wherein thermal energy is supplied to the said withdrawn gas prior to expansion.
4. The method defined in claim 1 wherein the mixed gases subjected to separation have a relative volatility in the absorbing liquid of not greater than 2: 1.
5. The method defined in claim 1 wherein the mixed gases subjected to separation have a relative volatility in the absorbing liquid of not greater than :1.
6. In the separation of mixed gases of different solubilities by preferential absorption of the more soluble gas in a liquid absorbent flowing in countercurrent contact with the mixed gases in a fractionating zone under pressure, the improvement of recovering the potentially available work otherwise consumed in the irreversible absorption of tops gas from said fractionating zone in lean liquid absorbent at the pressure of said fractionating zone, which comprises expanding said tops gas to a lower pressure with the performance of work, contacting said lean liquid absorbent with the expanded gas at said lower pressure to dissolve part of said expanded gas in said lean liquid absorbent, supplying said liquid absorbent containing dissolved gas to said fractionating zone, and recovering the work performed in expanding said tops gas.
7. In the separation of mixed gases of different solubilities by absorption in a stream of absorbing liquid in which the solubility of the gases increases materially With pressure, and wherein the stream of mixed gases is continuously passed in countercurrent contacting relationship with a stream of absorbing liquid under an elevated pressure in a fractionating zone, the gases withdrawn from the top portion of said fractionating zone after passage therethrough, the enriched liquid absorbent subjected to pressure release to separate the dissolved gas, and the lean liquid returned to the top portion of the fractionating zone, the improvement which comprises at least partially saturating said lean liquid with said withdrawn product gas by expanding with the performance of useful work such gas to a plurality of successively decreasing intermediate pressure levels between the pressure of the fractionating zone and that minimum pressure at which the absorbing liquid will dissolve such gas and by dissolving a portion of the gaseous stream at such intermediate pressure levels in the stream of lean liquid under relatively reversible conditions in the order of increasing pressure, charging thus partially saturated liquid as absorbing liquid feed to the fractionating zone, and recovering the useful work of expansion.
8. The method defined in claim '7 wherein the gases subjected to separation are at least semipermanent gases.
9. Apparatus for the separation of mixed gases of different solubilities by fractionating enrichment of a stream of said gases flowing in countercurrent contacting relationship under pressure, with a stream of absorbing liquid effective to preferentially absorb relatively more soluble gas, including fractionating means for conducting said stream of mixed gases under pressure in countercurren-t contacting relationship with a stream of absorbing liquid, a plurality of expansion engines eifective to recover useful mechanical work from expanding gas, means for supplying eiliuent undissolved gas from said fractionating means to said expansion engines in successive series relationship, means for dissolving expanded gas from a succeeding expansion engine in lean absorbing liquid to effect at least partial saturation thereof, means thereafter for dissolving additicnal expanded gas from a preceding expansion engine in said partially saturated absorbing liquid, and means for introducing thus partially saturated absorbing liquid as liquid absorbent to said fractionating zone as aforesaid.
10. The apparatus specified in claim 9 wherein a plurality of said engines are associated to deliver their combined output of :usefulmeohanical work to a single drive-means.
11. In the separation of mixedgasesof difierent solubilities by preferential absorption of the more soluble gas in a liquidabsorbent flowing in countercurrent contact with said mixed gases in a fraetionating zone under elevated pressure, said separation involving withdrawal of unabsorbed tops gas from said fractionating zone, decompression of enriched liquid'absorbent-to release absorbed gas therefrom, and'return of the resulting lean liquid absorbent to said fractionating zone,
the improvement of absorbing said" tops gas in said lean liquid absorbent under relatively reversible conditions prior-to the-return of said liquid absorbent to said fraotionating zone, which oomprises expanding with the performance of work said tops gas to an intermediate. pressure between that of said fractionating zone and that to which the enriched liquid absorbent is decompressed, eifecting absorption of the expanded gas in said lean liquid absorbent at-said intermediate pressure, and recovering the work performed in expanding said tops gas.
12. The method defined in claim 11 wherein the 5 tops gas is heated'prior to the expansion thereof.
13. :The method'defined in claim 11 wherein the sorbent are carried out in a plurality of stages-of successively lower pressure.
14., The method defined in claim 13 wherein the tops gas is heated prior to each expansion thereof.
MANSON BENEDICT.
References Cited in the file of this patent UNITEDSTATES' PATENTS Number Name Date 1,769,69 8 "Laird. July 1, 1930 2,015,223 'Horsley Sept.24, 1935 2,059,494, fShiras Nov. 3, 1936 2,219,529 Pyzel Oct. 29, 1940 2,241,717 Robinson et a1 May 13, 1941 2,316,744 Mellett et,a1., Apr. 13, 1943 FOREIGN PATENTS Number Country Date 097,603 Germany Oct. 19, 19 10 OTHER .REFERENCES Refiner and Natural Gasoline Manufacturer, v01. 21, 'No. 6, pages to 75.

Claims (1)

1. IN THE SEPARATION OF MIXED GASES OF DIFFERENT SOLUBILITIES BY CONTINUOUS FRACTIONATING ABSORPTION IN CONTACT WITH A STREAM OF ABSORBING LIQUID UNDER CONDITIONS INCLUDING A PRESSURE EFFECTIVE TO CAUSE SELECTIVE ENRICHMENT OF THE ABSORBED GASES IN THE MORE SOLUBLE COMPONENT OF THE SAID MIXED GASES, FOLLOWED BY DISENGAGEMENT OF ABSORBED GAS FROM THE ABSORBING LIQUID, AND RETURN OF THE LEAN ABSORBING LIQUID FOR FRACTIONATION OF SAID MIXED GASES, THE STEPS WHICH COMPRISE PASSING SAID MIXED GASES IN A FRACTIONATING ZONE UNDER PRESSURE IN CONTACTING RELATION TO THE ABSORBING LIQUID, WITHDRAWING UNDISSOLVED GAS FROM THE ABSORBING LIQUID AFTER CONTACT THEREWITH
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US2977386A (en) * 1955-04-08 1961-03-28 Allied Chem Absorption of formaldehyde in alkaline urea solution
US3260058A (en) * 1962-05-09 1966-07-12 Air Prod & Chem Method and apparatus for separating gaseous mixtures, particularly helium-containing gases
US4198388A (en) * 1978-02-14 1980-04-15 Bethlehem Steel Corporation Selective removal of H2 S from an H2 S and CO2 containing gas stream
US4198386A (en) * 1978-02-14 1980-04-15 Bethlehem Steel Corporation Selective removal of a gaseous component from a multi-component gas stream
US4394219A (en) * 1980-06-23 1983-07-19 Merix Corporation Fractionating liquids
US4574005A (en) * 1982-03-29 1986-03-04 Nordson Corporation Continuous coater solvent recovery process
US4602923A (en) * 1984-04-03 1986-07-29 Erwin J. Baumgartler Apparatus for degasifying a liquid medium
US20080223214A1 (en) * 2007-03-16 2008-09-18 Air Products And Chemicals, Inc. Method And Apparatus For Separating Gases
US20190195536A1 (en) * 2016-06-22 2019-06-27 Samsung Heavy Ind. Co., Ltd Fluid cooling apparatus

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US1769698A (en) * 1927-06-10 1930-07-01 Heat Treating Company Process for recovering natural gasoline
US2015223A (en) * 1931-10-13 1935-09-24 Ici Ltd Recovery of ethylene
DE697603C (en) * 1935-01-26 1940-10-19 Linde Eismasch Ag Process for the separation of hydrocarbons
US2059494A (en) * 1935-07-25 1936-11-03 Shiras Russell Norman Method of rectification
US2241717A (en) * 1937-06-15 1941-05-13 Polymerization Process Corp Conversion of hydrocarbons
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Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2977386A (en) * 1955-04-08 1961-03-28 Allied Chem Absorption of formaldehyde in alkaline urea solution
US3260058A (en) * 1962-05-09 1966-07-12 Air Prod & Chem Method and apparatus for separating gaseous mixtures, particularly helium-containing gases
US4198388A (en) * 1978-02-14 1980-04-15 Bethlehem Steel Corporation Selective removal of H2 S from an H2 S and CO2 containing gas stream
US4198386A (en) * 1978-02-14 1980-04-15 Bethlehem Steel Corporation Selective removal of a gaseous component from a multi-component gas stream
US4394219A (en) * 1980-06-23 1983-07-19 Merix Corporation Fractionating liquids
US4574005A (en) * 1982-03-29 1986-03-04 Nordson Corporation Continuous coater solvent recovery process
US4602923A (en) * 1984-04-03 1986-07-29 Erwin J. Baumgartler Apparatus for degasifying a liquid medium
US20080223214A1 (en) * 2007-03-16 2008-09-18 Air Products And Chemicals, Inc. Method And Apparatus For Separating Gases
US8518155B2 (en) * 2007-03-16 2013-08-27 Air Products And Chemicals, Inc. Method and apparatus for separating gases
US20190195536A1 (en) * 2016-06-22 2019-06-27 Samsung Heavy Ind. Co., Ltd Fluid cooling apparatus
US11859873B2 (en) * 2016-06-22 2024-01-02 Samsung Heavy Ind. Co., Ltd Fluid cooling apparatus

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